Process for breaking petroleum emulsions



3,166,516 PRQCESS FOR BREAKING PETROLEUM EMULSIGNS Willard H. Kirkpatrick, Sugar Land, and Virgil L. Scale,

Houston, Tex., assignors to Nalco Chemical Company,

a corporation of Delaware No Drawing. Filed Oct. 28, 1960, Ser. No. 65,564

10 (Iiaims. (Cl. 252-344) This invention relates to new and useful chemical compositions having surface-active properties and capable of lowering the interfacial tension between water and oil, especially in water-in-oil emulsions. The invention relates particularly to the treatment of emulsions of mineral oil and water, such as petroleum emulsions commonly encountered in the production, handling and refining of crude mineral oil, for the purpose of separating the oil from the water. Also, the invention relates to the treatment of other water-in-oil type of emulsions wherein the emulsions are produced artificially or naturally and the resolution of the emulsions presents a problem of recovery or disposal. A particularly important aspect of the invention is concerned with the employment of the compositions of the invention in desalting.

This application is a continuation-in-part of our copending application Serial No. 635,579, filed January 23, 1957, now abandoned.

Petroleum emulsions are, in general, of the water-inoil type wherein the oil acts as a continuous phase for the dispersal of finely-divided particles of naturally occurring water or brines. These emulsions are often extremely stable and will not resolve on long standing. It is to be understood that water-in-oil emulsions may occur artificially resulting from any one or more of numerous operations encountered in various industries. The emulsions obtained from producing wells and from the bottom of crude oil storage tanks are commonly referred to as cut oil, emulsified oil, bottom settlings, and iiB'sii One type of process involves subjecting an emulsion of the water-inoil type to the action of a deemuls-ifying agent of the kind hereinafter described, thereby causing the emulsion to resolve and stratify into its component parts of oil and water or brine after the emulsion has been allowed to stand in a relatively quiescent state.

Still another type of process involves the use of a deemulsifying agent of the kind hereinafter described in refinery desalting operations. In the refining of many crude oils a desalting operation is necessary in order to prevent the accumulation of large deposits of salt in the stills and to prevent corrosion resulting from the decomposition of such salts under high still temperatures. In a typical desalting installation 5% to of fresh water is added to the crude oil charge stock and emulsified therein by means of a pump or through a ditferential pressure Valve. A deemsulifying agent is added and the threated oil permitted to stand in a quiescent state for relatively short periods of time allowing the saltladen water to stratify, whereupon it is bled oil to waste resulting in 90% to 98% removal of salt content. This operation is carried out continuously as contrasted with batch treating.

In desalting operations where petroleum emulsions are created artificially and then broken, the conditions employed are usually quite different from those used in breaking water-in-oil petroleum emulsions at the well. The temperature may range from 160 F. to 350 F. and are preferably around 190 F. to 210 F. The pressures are those which are developed by heating under autogenous pressures and may be, for example, 215 to 250 pounds per square inch gauge. The time of heating is United States Patent 0 subject to variation but is usually around 15 to 30 minutes. Since a refinery unit may handle up to 50,000 barrels of oil per day and the amount of salt present may be, for example, 15 pounds to 250 pounds of salt per thousand barrels of oil, it will be appreciated that the separation of this salt is very important, especially since it is usually desired to reduce the salt content of the oil by at least One of the objects of the present invention is to provide a new and useful composition of matter which is water-wettable, interfacial and surface-active in order to enable its use as a deemulsifier or for such uses where surface-active characteristics are necessary or desirable.

A further object of the invention is to provide a new and improved process for resolving water in petroleum oil emulsions into their component parts of oil and water or brine.

An additional object of the invention is to provide a new and improved process for desalting petroleum oils.

Other objects will appear hereinafter.

In accordance with the invention, the crude oil deemulsifying agents are oxyalkylated condensation products obtained by reacting phenols which are primarily difunctional, alkyl phenols, the alkyl groups having an average of 4-15 carbons, formaldehyde, and alkylene polyamines. Ortho, orthoor para-, ortho-dialkyl phenols are not suitable for compositions of this invention, but amounts up to 25% of said dialkyl phenols in the difunctional, alkyl phenol reactant may be tolerated. Dialkyl phenols with one alkyl group in the orthoor para-position and one alkyl group in the meta-position are difunctional phenols for the purposes of this invention. The term difunctional phenol" relates to the methylol-forming reactivity of the phenol with formaldehyde.

The preferred alkylene polyamines are those having two primary amino groups, e.g., ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, higher polyalkylene polyamine homologs thereof up to about 10 amino groups per molecule, mixtures thereof, and the corresponding 1,2- and 1,3-polypropylene polyamines. The terminal amino groups of the alkylene polyamines, however, may be secondary amino groups such as those in N-substituted alkyl (1-8 carbons) phenyl or benzyl alkylene polyarnines.

The preferred phenols used in the condensate polymers are monoalkyl phenols having the alkyl group in the functional positions of the phenolic ring upon which methylol groups form in the reaction with formaldehyde, i.e., the orthoor para-positions. The alkyl groups in the phenolic substituent may be the same or they may be different, as when a mixture of alkyl phenols is the phenolic reactant. The average number of carbons in the alkyl groups of the phenolic reactant should be in the range of about 4-15. Alkyl groups of 4-9 carbons are preferred.

Examples of such phenols are o-butyl phenol, o-isobutyl phenol, p-n-butyl phenol, p-isobutyl phenol, p-tert. butyl phenol, o-amyl phenol, p-amyl phenol, p-tert. amyl phenol, o-octyl phenol, p-octyl phenol, o-nonyl phenol, p-nonyl phenol, o-dodecyl phenol, p-dodecyl phenol, mixtures of o-phenols and p-alkyl phenols, mixtures of ortho or para alkyl phenols with up to 25 0-, p-dialkyl phenols with 4-15 carbons in the alkyl groups such as the commercially available mixture of about 90% p-nonyl phenol with about 10% 0-, p-dinonyl phenol, and mixtures of difunctional monoalkyl phenols whose alkyl groups average at least about 4 carbons and not more than about 15 carbons, e.g., mixtures of p-octyl phenol and p-nonyl phenol, a mixture of about 30% p-isopropyl phenol and 7 0% p-octyl phenol, and the like.

The oxyalkylating agents are lower alkylene oxides, e.g.,

ethylene oxide, 1,2-propylene oxide, or mixtures of ethylene oxide and 1,2-propylene oxide and the weight ratio of the alkylene oxide to the phenol-formaldehyde-polyamine condensation product will, for most applications, fall between about 2:3 and :1, or even higher, respectively. The phenol-formaldehyde-polyamine condensation products contain about 4 to phenolic nuclei per resin molecule.

Where both ethylene oxide and propylene oxide are used to oxyalkylate the condensation product, they may be reacted as a mixture or the oxide may be added sequentiallye.g., the propylene oxide being added to the resin first and the ethylene oxide being added to the oxypropylene-1,2 groups. In the latter case, the terminal oxyalkylate groups are those of oxyethylene, which have primary hydroxyl groups. Simultaneous reaction of a mixture of the oxides probably gives an oxyalkylated product having both types of terminal hydroxy groups,

PHENOL-FORMALDEHYDE-POLYAMINE CONDENSATION The phenol-formaldehyde-alkylene polyamine conden sation products are prepared by reacting formaldehyde or a substance which breaks down to formaldehyde under reaction conditions, e.g., paraformaldehyde or trioxane, the difunctional alkyl phenol, often preferably a crude mixture of alkylated phenols for economic reasons, and the alkylene polyamine by heating the reactants in the presence of a small amount of an alkaline catalyst such as sodium hydroxide under the reaction temperatures and conditions causing the elimination of water of reaction. The condensates are phenolic and alkylene polyamine residues connected by methylene bridges. In some cases, the polyamine itself serves as the alkaline catalyst.

The condensation reaction preferably is carried out under substantially anhydrous conditions-excepting the water produced during the reaction. The aqueous distillate which begins to form when the reactants are heated is collected and removed from the reaction mixture.

The phenol formaldehyde polyamine condensation product may be prepared by agitating and heating a mixture of the three reactants. In this case, the presence of the polyamine provides sutficient alkalinity for the condensation reaction. Alternatively, the alkyl phenol and formaldehyde may be only partially condensede.g., by heating these reactants above for a shorter period of time than necessary to obtain complete condensation and leaving in the reaction mixture some unreacted phenol and formaldehyde. The reaction mixture is then cooled somewhat, and the alkylene polyamine is added to the reaction mixture. Heat is again applied to remove the water of reaction. Heating is continued until the amount of aqueous distillate collected indicates that the condensatiog is complete. Alternatively, the alkyl phenol may be precondensed with a portion of the formaldehyde in the form of precursor phenol-formaldehyde intermediate condensate. The intermediate condensate is thereafter further condensed by reacting it with the remainder of the formaldehyde and the alkylene polyamine thereafter added to the precursor condensate.

This aspect of the invention is illustrated in the following examples, but is not limited thereto.

Example A In a three-necked reaction flask provided with means of mechanical stirring and a return condenser system permitting the removal of any aqueous phase formed in the course of the reaction, there is added 750 parts of a crude alkylate phenol which comprises an undistilled p-nonyl phenol containing approximately 10% of o,pdinonyl phe- I101, 100 parts paraformaldehyde and 2 parts of finelydivided sodium hydroxide which is present as a catalyst in the reaction. These materials are heated to 60 C., and at this point the source of heat is removed. The temperature rises slowly to approximately C., at which point it is held for two hours. At this point 250 parts of a suitable hydrocarbon extract is added, and heat is applied to remove 36 parts of aqueous distillate at a maximum temperature of 150 C. The reaction mass is cooled to C., and at this point is added 100 parts of a crude mixture of polyethylene polyamines, approximately 10% of which is triethylenetetramine, 40% tetraethylene-pentamine and the remainder homologs higher than tetraethylene pentamine. Heat is again applied to remove 22 parts of aqueous distillate with a maximum final temperature of 220 C. At this point the material is cooled to 150 C., and 250 parts of a suitable hydrocarbon extract is added to give the finished phenolformaldehyde-alkylene polyamine resin.

Example B In a manner similar to Example A, 750 parts of the same crude alkylate phenol, 110 parts paraformaldehyde and 2 parts sodium hydroxide were heated for 2 hours at temperatures in the range of l00-110 C. After this period of heating, 250 parts of a suitable hydrocarbon extract were added, and 36 parts of aqueous distillate were removed with a maximum final temperature of C. The reaction mass was then cooled to 90 C., and 50 parts of diethylenetriamine were added. The material was again heated to remove an additional 32 parts of aqueous distillate with a maximum final temperature of 210 C. The material was cooled to C., and 250 parts of a suitable hydrocarbon extract were added to give the finished resin.

Example C In a manner similar to Example A, 750 parts of the same crude alkylate phenol, 120 parts of paraformaldehyde and 2 parts sodium hydroxide were reacted for a period of 2 hours at temperatures between 100-110 C. After this period of heating, 250 parts of a suitable hydrocarbon extract were added and the temperature raised to remove 36 parts of aqueous distillate with a maximum temperature of 136 C. The material was cooled to 100 C., and at this point 60 parts of the crude mixture of higher polyethylene polyamines, as described in Example A, were added. The reaction mass was again further heated to remove an additional 36% parts of aqueous d-istillate with a maximum final temperature of 212 C. The material was then cooled to 150 C., and 250 parts of a suitable hydrocarbon extract were added to give the finished resin.

Example D In a manner similar to Example A, 3750 parts of crude I alkylatephenol, 700 parts paraformaldehyde and 20 parts Example E In a three-necked reaction flask provided with means of mechanical stirring and a return condenser system permitting the removal of any aqueous phase formed in the course of reaction, there is added 500 parts of the crude alkylate phenol, as described in intermediate Example A, and 70 parts of diethylenetriamine. These materials are heated together to approximately 60 C. at which point the addition of paraformaldehyde is begun. Then 108 parts paraformaldehyde are added slowly and in portions in such a manner to maintain the temperature of the reaction mass below 90 C. After the addition of the para- In a manner similar to Example E, 500 parts of the crude alkylate phenol and 103 parts of diethylenetriamine are reacted With 120 parts of paraformaldehyde. After the addition of the paraformaldehyde is completed, 200 parts of a suitable hydrocarbon extract are added and the temperature raised to remove 69 parts of aqueous distillate with a maximum final temperature of 176 C. This gives the finished resin.

In the above example it might be noted that the ratio of amine to phenol provides about one primary amino group per mole of phenol. Also, as in Example E, the amine functions as a reactive catalyst.

The alkylene polyamine serves as a linking radical in the polymer chain, connected at two amino nitrogens by a methylene group, supplied by the formaldehyde, to the phenolic nuclei and possibly partly to other alkylene polyamine groups. With alkylene polyamines containing two terminal primary amino groups, such as those heretofore named, the reaction with formaldehyde in all probability is at the terminal primary amino groups.

The ratio of the phenol to the alkylene polyamine in the polymer condensate ranges from aboutlzl to about :1, respectively, and the molar quantity of the reacted aldehyde is in the range of about 0.9 to about 1.5 times the total reacted mols of the phenol and the alkylene polyamiue. With polyamines containing only 2, 3, or 4 amino groups, the mo] ratio of phenol to polyamine preferably ranges from about 1:1 to 4:1, respectively. At least some phenol and polyamine residues in all of the various types of condensates will be linked by the characteristic group,

R2 wherein R is the alkyl group in the 0- or p-position, the methylene bridge is in the o or p-position, and R is the remainder of the polyamine residue. Some of the polymeric condensates will have at least one of the following linking groups a) OH OH wherein the methylene bridge in (a) and R and R are as above-described. In all of the condensates, at least a portion of the alkylene polyamine residues are chemically combined internally in the structure of the phenol-formaldehyde-alkylene polyamine resins.

OXYALKYLATION OF THE CONDENSATION PRODUCTS Having prepared the intermediate phenol-formaldehyde-polyamine condensation products, the next step is the oxyalkylation of the condensation product. This is achieved by mixing the intermediate phenol-formaldehyde-polyamine condensation product in a hydrocarbon solvent with a small amount of sodium or potassium hy droxide in an autoclave. The condensation product is heated above 100 C., and preferably not over 180 C., and the alkylene oxide is charged into the autoclave until the pressure is in the vicinity of 75 to 100 p.s.i.

The reaction mixture is gradually heated until an exothermic reaction begins. The external heating is then removed, and alkylene oxide is added at such a rate that the temperature is maintained between about 150-160 C. in a pressure range of to p.s.i. After all of the alkylene oxide has been added, the temperature is maintained for an additional 10 to 20 minutes to assure substantially complete reaction of the alkylene oxide. The resulting product is the alkylene oxide adduct of an alkyl phenol-formaldehyde-polyamine condensation product, in which the weight ratio of the oxide to the condensation product is between about 2:3 and 10:1, respectively, or even slightly higher.

Some preferred embodiments of the oxyalkylated, alkyl phenol-formaldehyde-polyamine condensation products and methods of their preparation are illustrated in the following examples wherein all parts are by weight unless otherwise stated, but the invention is not limited thereto.

Example I In an autoclave having a nominal capacity of 5 gallons, equipped with a means of external heating, cooling and mechanical agitation, there is charged 22 parts of the resin of Example D. Into a transfer bomb there is charged 25 parts ethylene oxide. The reactants are heated to C., and the ethylene oxide is added until the reactor pressure is 30 p.s.i. The reaction mixture is grad ually heated until an exothermic reaction begins to take place. The external heating is then removed, and ethylene oxide is added at such a rate that the temperature is maintained between ISO- C. with a pressure range of 80 to 100 p.s.i. After approximately two hours, 22 parts of ethylene oxide have been added to the autoclave, and the temperature is maintained for an additional 30 minutes to make sure that the unreacted oxide is reduced to a minimum. The resulting product is the ethylene oxide adduct of a phenol-formaldehyde-alkylene polyamine resin in which the ratio of oxide to resin by weight is about 1 to 1.

Example [I In a manner similar to Example I, a mixed oxide adduct of the resin of Example D was prepared in which the ratio of ethylene oxide to propylene oxide was 1 to 1. The finished product is a material in which the ratio of mixed oxides to resin is 6 to 1.

Example III In a manner similar to Example I, a mixed oxide adduct of the resin of Example D was prepared in which the ratio of ethylene oxide to propylene oxide is 1 to 2. The finished product contains a ratio of 6 parts of mixed oxides to 1 part of resin.

Example IV In a manner similar to Example I, 4 pounds of the resin of Example D and 1 part of sodium hydroxide are charged into a 5 gallon autoclave. These materials are heated to 145 C., and 36 pounds of propylene oxide are added over a period of approximately 8 hours at temperatures in the range of 145150 C. and pressures in the range of 60-80 p.s.i. After the addition of the propylene oxide was completed, the material was further heated for a period of 2 hours so that residual propylene oxide is reduced to a minimum. The finished product is a propylene oxide adduct of the phenol-formaldehyde-polyamine resin in which the ratio of propylene oxide to resin is 9 to 1.

Example V In a manner similar to Example I, 8 pounds of the finished product of Example IV are charged into a gallon autoclave. At temperatures between ISO-160 C., 2 pounds of ethylene oxide are added, and the material is further heated for a period of 30 minutes to allow the reactor pressure to drop to a constant value. The finished product is a sequential propylene oxide-ethylene oxide adduct of a phenol-formaldehyde-polyamine resin in which the ethylene oxide content is by weight.

Example VI In an autoclave having a 2-liter capacity, equipped with a means of external heating, internal cooling coils and mechanical agitation, there is charged 400 parts of the resin of Example B and 1 part sodium hydroxide. Into a transfer bomb there is introduced 605 parts ethylene oxide. The resin intermediate is heated to 140 C., and ethylene oxide is charged into the reactor until reactor pressure is 80 p.s.i. The reaction mixture is gradually heated until an exothermic reaction begins to take place. The extenral heating is then removed, and ethylene oxide is added at such a rate than the temperature is maintained between 150-160 C. with a pressure range of 80-100 p.s.i. After approximately 3 hours all of the oxide has been added to the autoclave, and temperature is maintained for an additional minutes to make certain that the unreacted oxide is reduced to a minimum. The resulting product is the ethylene oxide adduct of a phenol-formaldehyde-polyamine resin in which the ratio of oxide to resin is 3 to 2 by weight.

Example VII In a manner similar to Example VI, 504 parts of the resin of Example A and 515 parts of ethylene oxide are reacted. 'Ihe finished product is the ethylene oxide adduct of a phenol-formaldehyde-polyamine resin in which the ratio of oxide to resin is 1 to 1 by weight.

Example VIII In a manner similar to Example VI, 600 parts of the resin of Example E was reacted with 400 parts of ethylene oxide which gives a finished product in which the ratio of oxide to resin is 2 to 3 by weight. The oxyalkylation catalyst used in this preparation was potassium hydroxide.

Example IX In an autoclave having a two-liter capacity, equipped with a means of external heating, internal cooling coils and mechanical agitation, there is charged 400 parts of the resin of Example E and 2 parts sodium hydroxide. Into a transfer bomb there is introduced 300 parts of the ethylene oxide and 900 parts propylene oxide. The resin is heated to 145 C., and the mixed oxides are charged into the reactor until reactor pressure is 60 p.s.i. The reaction mixture is gradually heated until an exothermic reaction begins to take place. The external heating is then removed, and the mixed oxides are added at such a rate that the temperature is maintained between 145l50 C. with a pressure range of 80-100 p.s.i. After approximately 4 hours all of the oxide has been added to the autoclave, and the temperature is maintained for an additional 2 hours to make certain that the unreacted oxide is reduced to a minimum. The resulting product is the mixed oxide adduct of a phenol-formaldehyde-polyamine resin in which the ratio of mixed oxides to resin is 3 to 1 by weight.

Example X In an autoclave having a two-liter capacity, equipped with means of external heating, internal cooling coils and mechanical agitation, there is charged 700 parts of the resin of Example F and 2 parts potassium hydroxide. Into a transfer bomb there is introduced 700 parts propylene oxide. The intermediate is heated to 135 C., and

the propylene oxide is charged into the reactor until reactor pressure is psi. The reaction mixture is gradually heated until an exothermic reaction begins to take place. The external heating is then remcwed, and propylene oxide is then added at such a rate that the temperature is maintained between 135145 C. witha pressure range of 6080 p.s.i. After approximately 6 hours all of the propylene oxide has been added to the autoclave, and the temperature is maintained for an additional 2 hours to make certain that the unreacted propylene oxide is reduced to a minimum. The resulting product is the porpylene oxide adduct of a phenol-formaldehyde-polyamine resin in which the ratio of oxide to resin is 1 ml by weight.

Example XI hyde-polyamine resin in which there is 10% of ethylene oxide by weight.

Example XII In a manner similar to Example I, an ethylene oxide adduct of a resin of Example C was prepared in which the ratio of oxide to resin is 2 to 3 by weight.

The oxyalkylated phenol-formaldehyde-alkylene polyamine resins of the foregoing examples are made into finished products suitable for use as emulsion-breaking chemicals by blending the resins with about an equal amount by weight of a suitable hydrocarbon vehicle.

Among the suitable hydrocarbon vehicles which can be employed as diluents is sulfur dioxide extract. This material is a by-product from the Edeleanu process of refining petroleum in which the undesirable fractions are removed by extraction with liquid sulfur dioxide. After removal of the sulfur dioxide a mixture of hydrocarbons, substantially aromatic in character, remains and is designated in the trade as sulfur dioxide extract of S0 extract. Examples of other suitable hydrocarbon vehicles are toluene, xylene, gas oil, diesel fuel, bunker fuel and coal tar solvents. The above cited examples of solvents are adaptable to azeotropic distillation as would also be any other solvent which is immiscible with water, miscible with the reacting mass and has a boiling point or boiling range in excess of the boiling point of water.

De-emulsification of water-in-oil emulsions The compositions of this invention are surface-active and are particularly suitable for the de-emulsification of naturally-occurring crude oil emulsions and emulsions resulting from the aforedescri'bed desalting processes. Deemulsification is achieved by mixing the de-emulsifying agents of this invention, at a ratio in the approximate range of one part of the de-emulsifying agent to 2,000- 50,000 parts of the emulsion, and thereafter allowing the emulsion to remain in a relatively quiescent state during which separation of the oil and water occurs. With naturally-occurring emulsions, the temperature of the emulsion, may be 50-210 F., although temperatures of at least F. are often preferred to accelerate separation of the de-emulsified water and oil phases. The deemulsifying agents of this invention may be used in conjunction with other de-emulsifying agents form classes such as the petroleum sulfonate type, of which naphthalene sulfonic acid is an example, the modified fatty acid type, and others.

The effectiveness of the compositions of this invention as de-emulsifying agents is illustrated in the following tests and data.

BOTTLE TESTING OF CRUDE OIL EMULSIONS The bottle testing of crude oil emulsions is conducted according to the following procedure: Fresh samples of the emulsion-breaking chemicals in organic solvent solu tion are prepared in 10% solutions. These solutions are made by accurately diluting 10 milliliters of the emulsionbreaking chemicals in 90 milliliters of a mixture of equal parts of anhydrous isopropyl alcohol and an aromatic hydrocarbon such as xylene. The mixture is agitated well until the emulsion-breaking chemical is completely dissolved.

The equipment for running the crude oil emulsionbreaking test, in addition to the foregoing 10% solutions, includes a set of six ounce graduated prescription bottles, a funnel, a graduated 0.2 milliliter pipette, a thief pipette, a centrifuge, centrifuge tubes and a thermometer. The graduated prescription bottles are filled to the 100 milliliter mark with the crude oil emulsion to be tested, preferably a sample which has been recently collected. If there is any free water in the crude oil emulsion sample collected, it is bled off before the bottles are filled. Each bottle is inverted several times with the thumb over the opening of each bottle so that the bottle will be coated with an emulsion film.

By means of the 0.2 milliliter pipette, the prescribed volume of the 10% solution of the emulsion-breaking chemical is added to the emulsion in the bottles. The bottles are then capped and given manual agitation for a predetermined number of counts. .The number of counts are determined by a survey of the agitation which can be secured in the system in which the crude oil emulsion is being used. ment, the bottles are placed in hot water bath, the length of time and temperature determined by the particular plant equipment and practice in which the particular emulsion is employed. If the plant provides for hot agitation of the emulsion the bottles may be given a corresponding amount of manual hot agitation.

The bottles are then removed from the hot water bath and the water drop, presence of the bottom settlings (13.8.) layer and color and general appearance of the oil are noted.

A thief grind-out is taken on all bottles which appear to be promising. A thief grind-out is made by preparing centrifuge tubes filled with gasoline to the 50% mark. The thief pipette is set to the proper length by adjusting the rubber stopper so that the bottom of the pipette is about /2 inch above the oil-water level of the bottle with maximum water drop. This same setting is used for all subsequent thiefings on remaining bottles. The thiefed oil from each bottle is added to the centrifuge tube to the 100% mark, and the tube is shaken. The samples are then centrifuged for three minutes.

With certain parraffin base oils a portion of the parafi'in is thrown down with the 13.8. If the centrifuge tubes are heated to 150 F. the paraffin will melt and be dissolved in the gasoline-oil mixture and usually will not be thrown down again with the BS. upon centrifuging while hot. However, occasionally the parafiin will re-congeal as the tube cools during centrifuging. If this occurs, the tube is removed from the centrifuge and heated to 150 F. without shaking or disturbing the settled 13.8. layer. The heated sample is then centrifuged for seconds. This should given a true B.S. reading free of paratlin.

An excess chemical grind-out is then run on each centrifuge tube by adding several drops of a solution in white gasoline or other solvent of a chemical which causes complete separation of the water and oil. With some sensitive emulsions the chemical will cause reemulsiiication. In these instances it is necessary to rethief and add a lesser amount. Each tube is vigorously shaken to make sure that the packed B.S. layer is broken up and the tubes heated to 150 F. in the case of troublesome parafiin base crude oil. The samples are then centrifuged for three minutes.

During the test the speed of the water drop is observed carefully after the emulsion-breaking chemical is added If the emulsion requires heat for treatto the prescription bottles. The observation of the color and brilliance of the oil in transmitted light is very important. In general, the brilliance and depth of color increases with a decrease in B.S. & W. (bottom settlings and water) content. The observations of color are made in the oil in the prescription bottle before and after heat treatment. In the ideal treatment of crude oil emulsions the oil-water line could be a sharp, clean line without any web or sludge present. Presence of a considerable amount of sludge or web is undesirable because this foreign material will eventually go to stock in the treating plant and be reported as 13.8. Traces of web or sludge, however, will disappear or be removed in the normal treating plant.

In almost all instances the thief grind-out and excess chemical grind-out readings indicate the formula that has most nearly produced crude oil free from 3.8. and water. The most efiicient emulsion-breaking chemical is determined by the foregoing test procedure by the overall consideration of the following factors: relative speed of the breaking of the emulsion which is usually indicated by speed of water drop, color and brilliance of the oil layer, the relative absence of web or sludge at oil-water line and the ability to most nearly produce treated oil that is free from 8.8. and water.

By way of illustrating the effectiveness of the emulsionbreaking chemicals contemplated by this invention, the composition of Example VI and a composition similar to that of Example VI but having a ratio of ethylene oxide to resin of 1:1, identified in the following table as Composition A and Composition B, respectively, were tested as solutions of between 4 and 5 percent of active ingredient according to the foregoing bottle-testing procedure on samples of 27 gravity crude oil obtained from South Mountain Field, California. The crude oil emulsion contained about eight percent water. The solutions were added at a ratio of 0.08 part of a 10% solution, as described in the foregoing procedure, to parts of emulsion fluid. The samples were given 200 shakes cold and 100 shakes hot, the hot temperature being 180 F. The observations made during the tests were recorded and are summarized in the following table.

TABLE I Water Drop Thief Excess Grind-Out Grind-Out Treating Chemical 14 hr. 13.8. Water 13.8. Water min.

Composition A 2 6 1 2 0 0 l. 0 Composition B 2 8 O 1 0.2 0 0. 2

Before hot agitation. 2 After hot agitation.

The composition of Example VII has been found to be effective in desalting operations.

It is to be noted that in the de-emulsifying agents of this invention wherein ethylene oxide is employed as the oxyalkylating agent, the Weight ratio of ethylene oxide to resin is at the lower end of the range heretofore described and preferably does not exceed a ratio of about 2:1. At higher ratios, these compounds are too hydrophilic to be used as emulsion-breaking chemicals.

The invention is hereby claimed as follows:

1. A process for breaking a petroleum oil emulsion of the water-in-oil type which comprises breaking said emulsion by subjecting said emulsion to the action of a polyoxyalkylated alkyl phenol-formaldehyde-alkylene polyamine resin, said resin being formed by the polycondensation of a mixture selected from the group consisting of (A) said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, and (B) a precondensate of said alkyl phenol and formaldehyde, said alkyl phenol monomer, said formaldehyde, and said wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the -OH group, and R is the monovalent residue of the alkylene polyamine, the oxyalkylene groups of said oxyalkylated resin having a number of carbons in the range of 2-3, and the weight ratio of oxyalkylene groups to resin being between about 2:3 and 10:1, respectively, and separating the oil and water phases of the broken emulsion.

2. A process for breaking a petroleum oil emulsion of the water-in-oil type which comprises breaking said emulsion by subjecting said emulsion to the action of a polyoxyethylated alkyl phenol-formaldehyde-alkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde,

and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75% difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively, at least a part of the phenol and the polyamine being combined in the resin structure by the grouping where R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene polyamine, and the weight ratio otoxyethylene groups to resin being between about 2:3 and 2:1, respectively, and separating the oil and water phases of the broken emulsion.

3. A process for breaking a petroleum oil emulsion of the water-in-oil type which comprises breaking said emulsion by subjecting said emulsion to the action of a polyoxypropylated alkyl phenol-formaldehyde-alkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75 difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10: 1, respectively, at least a par-t of the phenol and the polyamine being combined in the resin structure by the grouping CHr-NHR 1- wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and

R is the monovalent residue of the alkylene polyamine, and the weight ratio of oxypropylene groups to resin being between about 2:3 and 10:1, respectively, and separating the oil and water phases of the broken emulsion.

4. A process for breaking a petroleum oil emulsion of the Water-in-oil type which comprises breaking said emulsion by subjecting said emulsion to the action of a polyoxyalkylated alkyl phenol-formaldehyde-alkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, thelatter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least difunctional alkyl phenol with the alkyl groups of the alkyl phenol having at average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively, at

least a part of the phenol and the polyamine being combined in the resin structure by the grouping wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the -OH group, and R is the monovalent residue of the alkylene polyamine, the oxyalkylene groups consisting of both oxyethylene groups and oxypropylene groups in heteric arrangement in the oxyalkylene chains on said oxyalkylated resin, the weight ratio of oxypropylene groups to oxyethylene groups being not greater than 4:1, respectively, and the weight ratio of oxyalklene groups to resin being between about 2:3 and 10:1, respectively, and separating the oil and water phases of the broken emulsion.

5. A process for breaking a petroleum oil emulsion of the water-in-oil type which comprises breaking said emulsion by subjecting said emulsion to the action of a polyoxyalkylated alkyl phenol-formaldehyde-alkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75 difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively, at least a part of the phenol and the polyamine being combined in the resin structure by the grouping (MEI CHr-NHRiwherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene polyamine, the oxyalkylene groups consisting of oxyethylene groups and oxypropylene groups with the oxyethylene groups positioned terminally in the polyoxyalkylene chains, and the weight ratio of oxyalkylene groups of resin being between about 213 and 10:1, respectively, and separating the oil and water phases of the broken emulsion.

6. A process for desalting a petroleum oil which comprises mixing a petroleum oil containing water soluble salts with water, subjecting the resultant mixture to the action of a polyoxyalkylated alkyl phenol-formaldehydealkylene polyamine resin, said resin being formed by the polycondensation of a mixture selected from the group consisting of (A) said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, and (B) a precond'en'sate of said alkyl phenol and formaldehyde, said alkyl phenol monomer, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75% difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4l5, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to :1, respectively, at least a part of the phenol and the polyamine being combined in the resin structure by the grouping CHz-NHRP' wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene polyamine, the oxyalkylene groups of said oxyalkylated resin having a number of carbons in the range of 2-3, and the Weight ratio of oxyalkylene groups to resin being between about 2:3 and 10:1, respectively, and separating the oil and water phases of said mixture.

7. A process for desalting a petroleum oil which comprises mixing a petroleum oil containing water soluble salts with water, subjecting the resultant mixture to the action of a polyoxyethylated alkyl phenol-formaldehydealkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75% difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively, at least a part of the phenol and the polyamine being combined in the resin structure by the grouping wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene polyamine, and the weight ratio of oxyethylene groups to resin being between about 2:3 and 2:1, respectively, and separating the oil and water phases of said mixture.

8. A process for desalting a petroleum oil which comprises mixing a petroleum oil containing water soluble salts with water, subjecting the resultant mixture to the action of a polyoxypropylated alkyl phenol-formaldehydealkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75 difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively,

"14 at least a part of the phenol and the polyamine being combined in the resin structure by the grouping wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene polyamine, and the weight ratio of oxypropylene groups to resin being between about 2:3 and 10:1, respectively, and separating the oil and water phases of said mixture.

9. A process for desalting a petroleum oil which comprises mixing a petroleum oil containing water soluble salts with water, subjecting the resultant mixture to the action of a po'lyoxyalkylated alkyl phenol-formaldehyde alkyiene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75% difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 415, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively, at least a part of the phenol and the polyamine being combined in the resin structure by the grouping wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene polyamine, the oxyalkylene groups consisting of both oxyethylene groups and oxypropylene groups in heteric arrangement in the oxyalkylene chains on said oxyalkylated resin, the weight ratio of oxypropylene groups to oxyethylene groups being not greater than 421, respectively, and the weight ratio of oxyalkylene groups to resin being between about 2:3 and 10:1, respectively, and separating the oil and water phases of said mixture.

10. A process for desalting a petroleum oil which comprises mixing a petroleum oil containing water soluble salts with water, subjecting the resultant mixture to the action of a polyoxyalkylated alkyl phenol-formaldehydealkylene polyamine resin, said resin being formed by the polycondensation of a mixture of said alkyl phenol, said formaldehyde, and said alkylene polyamine, the latter having two primary amino groups and 2-6 carbons per alkylene group, said alkyl phenol being at least 75% difunctional alkyl phenol with the alkyl groups of the alkyl phenol having an average number of carbons in the range of 4-15, the mol ratio of the phenol to the polyamine in said resin being in the range of 1:1 to 10:1, respectively at least a part of the phenol and the polyamine being combined in the resin structure by the grouping '15 wherein R is the alkyl group of the phenol and is in one of the positions ortho and para to the OH group, and R is the monovalent residue of the alkylene po'lyamine, the oxyalkylene groups consisting of oxyethylene groups and oxypropylene groups with the oxyethy-lene groups positioned terminally in the polyoxyalkylene chains, and the weight ratio of. oxyalkylene groups to resin being between about 2: 3 and 10: 1, respectively, and separating the oil and water phases of said mixture.

' References Cited in the file of this patent UNITED STATES PATENTS De Groote Nov. 30, 1954 De Groote Jan. 7, 1958 De Groote et a1 Mar. 25, 1958 De Groote et a1. Mar. 25, 1958 De Groote June 17, 1958 De Groote Sept. 20, 1958 UNITED STATES PATENT OFFICE. CERTIFICATE OF CORRECTION Patent No. 3,166,516 January 19, 1965 Willard H. Kirkpatrick et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 20 to 22, the formula should appear as shown below instead of as in the patent:

CH CH OH and CH CHCH column 4, line 27, for "90 C." read 90 C. column 7 line 22, for "extenral" read external column 8, line 66, for "form" read from column 9, line 62, for "given" read give column 16, under "UNITED STATES PATENTS", last line, for Sept. 20, 1958" read Sept. 30, 1958 Signed and sealed this 3rd day of August 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,166,516 January 19, 1965 Willard H. Kirkpatrick et a1.

It is hereby certified that'error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 20 to 22, the formula should appear as shown below instead of as in the patent:

CH CH OH and CH CHCH column 4, line 27, for "90 C." read 90 C. column 7, line 22, for "extenral" read external column 8, line 66, for "form" read from column 9, line 62, for "given" read give column 16, under "UNITED STATES PATENTS", last line, for "Sept. 20, 1958" read Sept. 30, 1958 Signed and sealed this 3rd day of August 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A PROCESS FOR BREAKING A PETROLEUM OIL EMULSION OF THE WATER-IN-OIL TYPE WHICH COMPRISES BREAKING SAID EMULSION BY SUBJECTING SAID EMULSION TO THE ACTION OF A POLYOXYALKYLATED ALKYL PHENOL-FORMALDEHYDE-ALKYLENE POLYAMINE RESIN, SAID RESIN BEING FORMED BY THE POLYCONDENSATION OF A MIXTURE SELECTED FROM THE GROUP CONSISTING OF (A) SAID ALKYL PHENOL, SAID FORMALDEHYDE, AND SAID ALKYLENE POLYAMINE, THE LATTER HAVING TWO PRIMARY AMINO GROUPS AND 2-6 CARBONS PER ALKYLENE GROUP, AND (B) A PRECONDENSATE OF SAID ALKYL PHENOL AND FORMALDEHYDE, SAID ALKYL PHENOL MONOMER, SAID FORMALDEHYDE, AND SAID ALKYLENE POLYAMINE, THE LATTER HAVING TWO PRIMARY AMINO GROUPS AND 2-6 CARBONS PER ALKYLENE GROUP, SAID ALKYL PHENOL BEING AT LEAST 75% DIFUNCTIONAL ALKYL PHENOL WITH THE ALKYL GROUPS OF THE ALKYL PHENOL HAVING AN AVERAGE NUMBER OF CARBONS IN THE RANGE OF 4-15, THE MOL RATIO OF THE PHENOL TO THE POLYAMINE IN SAID RESIN BEING IN THE RANGE OF 1:1 TO 10:1, RESPECTIVELY, AT LEAST A PART OF THE PHENOL AND THE POLYAMINE BEING COMBINED IN THE RESIN STRUCTURE BY THE GROUPING 